N-phenylthiocarbamoylthio-hydroximate pesticides

ABSTRACT

A CARBAMATE COMPOUND OF THE FORMULA:   (R&#39;&#39;-S-C(-R)=N-O-CO-N(-CH3)-S-),(X)N-BENZENE   WHEREIN X IS HYDROGEN, LOWER ALKYL, LOWER ALKOXY, NITRO OR HALOGEN, R AND R&#39;&#39; ARE EACH LOWER ALKYL AND N IS AN INTEGER OF 1 TO 5, WHICH IS USEFUL AS AN INSECTICIDE, A NEMATOCIDE AND AN ACARICIDE WITH LESS TOXICITY TO WARMBLOODED ANIMALS AND CAN BE PREPARED BY REACTING A BENZENESULFENYL HALIDE OF THE FORMULA:   (Z-S-),(X)N-BENZENE   WHEREIN X AND N ARE EACH AS DEFINED ABOVE AND Z IS HALOGEN WITH AN N-METHYLCARBAMIC ESTER OF THE FORMULA:   CH3-NH-CO-O-N=C(-R)-S-R&#39;&#39;   WHEREIN R AND R&#39;&#39; ARE EACH AS DEFINED ABOVE IN AN INERT SOLVENT IN THE PRESENCE OF A BASE AT A TEMPERATURE OF -10 TO 50*C.

United States Patent Oifice 3,825,579 Patented July 23, 1974 U.S. Cl. 260-453 R 7 Claims ABSTRACT OF THE DISCLOSURE A carbamate compound of the formula:

wherein X is hydrogen, lower alkyl, lower alkoxy, nitro or halogen, R and R are each lower alkyl and n is an integer of l to 5, which is useful as an insecticide, a nematocide and an acaricide with less toxicity to warmblooded animals and can be prepared by reacting a benzenesulfenyl halide of the formula:

wherein X and n are each as defined above and Z is halogen with an N-methylcarbamic ester of the formula:

wherein R and R are each as defined above in an inert solvent in the presence of a base at a temperature of to 50 C.

The present invention relates to novel carbamate compounds, and their preparation an duse. More particularly, it relates to carbamate compounds of the formula:

Xn CH: R wherein X is hydrogen, lower alkyl (e.g. methyl, ethyl, propyl, isopropyl, butyl), lower alkoxy (e.g. methoxy, ethoxy, propoxy, isopropoxy, butoxy), nitro or halogen (e.g. chlorine, bromine, iodine, fluorine), R and R' are each lower alkyl (e.g. methyl, ethyl, propyl, isopropyl, butyl) and n is an integer of 1 to 5, and their preparation and use.

In this specification, the term lower is intended to mean those having 1 to 4 carbon atoms.

As the results of the study on the pesticidal activity of various chemical compounds, it has been found that the said carbomate compounds (I) show an excellent insecticidal activity as well as a nematocidal activity and an acaricidal activity with less toxicity to warm-blooded animals. Thus, they are useful as pesticides against a wide variety of harmful organisms including insects, nematodes and mites.

According to the present invention, the cambamate compound (I) can be prepared by reacting a benzenesulfenyl halide of the formula:

n (II) wherein X and n are each as defined above and Z is halogen (e.g. chlorine, bromine) with an N-methylcarbamic ester of the formula:

0 CH3NH(UJON=C/ S-R (III) wherein R and R are each as defined above.

Examples of the benzenesulfenyl halide (H) are as follows:

S Cl CH3- S Cl C1 S Cl CH S Cl Examples of N-methylcarbamic ester (III) are as follows:

The reaction is usually effected in an inert solvent (e.g. benzene, toluene, xylene, ether, chloroform, carbon tetrachloride) in the presence of a base such as a tertiary organic amine (e.g. triethylamine, dimethylaniline, diethylaniline, pyridine, N-methylmorpholine) at a temperature from -10 to 50 C. The particularly preferred inert solvent and base are benzene and pyridine, respectively.

Typical examples of the carbamate compounds (I) prepared by the process of this invention are as follows:

As stated above, the carbamate compounds (I) exhibit a. strong insecticidal activity against various harmful insects, including those belonging to Hemipzera, Lepidoptera, Coleoptera and Diptera, as well as a nematocidal activity and an acaricidal activity against nematodes and mites. It is particularly notable that they exert their activities rapidly on Hemz'ptem insects (e.g. planthopper, leafhopper, aphid, bug) and larvae of midges which are carriers of various infectious diseases. Some of the test results, by which the favorable activities of the carbamate compounds (I) are evidenced, are shown below.

Test 1 TABLE 1 Mortality (percent) after- 1 day 4 days 7 days 11 days Compound number:

Test 2 A dust of Compound No. 1 or 3 prepared as in Example III was applied to rice plants 40 days after the emergence in pots by the use of a duster at a rate of 3 kg. per 10 ares. White-backed planthoppers (Sogatella fu-rcifera) were released thereto and covered by a glass cylinder. The knock down percent with the lapse of time was calculated. The results are shown in Table 2.

TABLE 2 Knock down, percent KTso 60 100 (min.)

Lapse oftime(min.)... 5 10 20 Compound number:

4 Test 3 To the root of rice plants grown in pots and being at the tillering stage, 6% granules of Compound No. 1 or 3 prepared as in Example IV were applied at a rate of 6 kg./ 10 ares. After 3 days, 30 adults of green rice leafhoppers were released thereto and covered by a net cage. The mortality was calculated after 24 hours. The results are shown in Table 3.

TABLE 3 Compound No.: Mortality (percent) 1 85.2 3 79.3

Test 4 In a beaker, 0.5 ml. of an aqueous dilution of a 40% emulsifiable concentrate of Compound No. 1, 3, 4 or 5 prepared as in Example I was admitted, and 0.5 ml. of water containing nematodes was added thereto. Adjusting the resultant mixture to make a designed concentration of the active compound, the death was observed microscopically 24 hours thereafter. The results are shown in Table 4.

TAB LE 4 Concentration Mortality (p.p.m.) (percent) Compound number:

1 500 3 500 96. 7 4 500 82. 1 5 500 75.0 0, O-diethyl 0-(4-dimethylsulfamoybphenylphosphorothioate 500 83. 3

Test 5 A 40% emulsifiable concentrate of Compound No. 1, 3 or 4 prepare as in Example I was diluted with water to make a designed concentration of the active ingredient, and 30 larvae of mosquito (Culex pipiens pallens) were released therein. After 24 hours, the mortality was recorded and the LC was calculated. The results are shown in Table 5.

TABLE 5 Compound No.: LC (p.p.m.) 1 0.37

Further, the carbamate compounds (I) are quite less toxic to warm-blooded animals. For instance, in the oral administration of Compound Nos. 1 to 5 in aqueous suspension to male mice at a rate of 500 milligrams per kilogram of body weight, no death was observed after 48 hours.

As ensured by these and other test results, the carbamate compounds (I) are useful for combatting 'various injurious insects, nematodes and mites, particularly in agriculture and household, with high safety to warm-blooded animals.

For the insecticidal use, the carbamate compound (I) is normally extended with an inert carrier to make a preparation form conventionally employed for insecticides such as emulsifiable concentrate, wettable powder, oil spray, dust, granule, aerosol, bait or the like. Examples of the inert carrier are talc, clay, bentonite, kaolin, diatomaceous earth, pyrophyllite, benzene, toluene, dimethylnaphthalene, aromatic naphtha, etc. Surfactants may be also used as spreaders or emulsifiers. When desired, there may be further incorporated other insecticidal agents such as chlorinated hydrocarbons (e.g. DDT, methoxychlor, benzene hexachloride, chlordane, toxaphene, heptachlor, aldrin, endrin), organic phosphorus compounds (e.g. phenitrothion, Surecide, CyanOX, malathion, demeton, tetraethyl pyrophosphate, S-alithion), carbamate compounds (e.g. Seven, 3,4-dimethylphenyl-N-methyl carbamate, Lannate) and pyrethroids (e.g. pyrethrin, allethrin, tetramethrin, S-benzyl-furfuryl chrystanthemate, barthrin), miticides, nematocides, microbicides, herbicides, fertilizers, soil disinfectants and the like.

Practical embodiments of the present invention are illustratively shown in the following examples. In these examples, parts are by weight.

Example 1 Example III Compound No. 3 (5 parts) and talc (95 parts) are mixed thoroughly and pulverized to make 5% dust. The dust is applied as such.

Example IV Compound No. 4 (6 parts), sodium ligninsulfonate (2 parts) and 200 mesh clay (92 parts) are mixed thoroughly in this order, kneaded with a small amount of water, granulated and then dried to make 6% granules. The granules are applied as such.

What is claimed is:

1. A carbamate compound of the formula thiohydroximate (Compound No. 1) in 90% yield. m 1.5863.

Example 2 E In the same manner as above, the following compounds I are prepared: Xn H: S-R' Product Starting material Compound Benzenesultenyl No. Carbamate compound (1) Physical data halide (II) N -Methy1carbamic ester (III) 1 CH; m 1.5863 CH i Cw w 1 '-0N= OHS-NHCON=C CH; scH; S-CH! 2 O CH: no 8 Same as above.

H CH s 01 3 o1 M.P. 82-84" C. 01 D l 0H. Cl-S1II-bO-N=C (Ii-@s Cl 4 01 M.P. 95-96 c. 01

l H I Do. CH.|'SIIIC-0N=C\ om- 01 CH: S-CH1 5 0 CH: M.P. 130-132 0. D =N s 01 0 OzN- S-Iil-C0 =C\ CH: S-CHI o 0 CH; "D 1.5823

s .Ii]'.. C o-N=C\ CH.\-NHC-ON=C CH; 8-01 3432B 7 (II) 0:11; no" 1. 845 Same as above 3 @S-IzI-C-O-N: CHr-NH-ii-Q-Nw CHI SC:H1 S CaH1 Example I wherein X is hydrogen, lower alkyl, lower alkoxy, nitro,

Compound No. 1 (40 parts), dimethylformamide (20 parts), cyclohexanone (20 parts) and a surfactant (trade name Sorpol 9049 manufactured by Toho Chemical Co., Ltd., Japan; 20 parts) are mixed thoroughly in this order to make 40%1 emulsifiable concentrate. The emulsifiable concentrate is diluted with water and then applied.

maple 11 chlorine or bromine, R and R are each lower alkyl and n is an integer of 1 to 3.

2. The carbamate compound according to claim 1, whereln X is hydrogen, R and R' are each methyl and n is 1- i l 3. The carbamate compound according to claim 1, wherein X is methyl, R and R are each methyl and n is 1. i

4. The carbamate compound according to claim 1, wherein X is chlorine, R and R are each methyl and n 5. The carbamate compound according to claim 1, wherein one X is methyl and the other X is chlorine, R and R are each methyl and n is 2.

6. The carbamate compound according to claim 1, wherein X is nitro, R and R are each methyl and n is 1.

7 ,8 7. A carbarnate compound of the formula: I I References Cited 6 UNITED STATES PATENTS 3,576,834 4/1971 Buchanan 260-566 AC 3,506,698 4/1970 "Jelinek 260-453 R @SNCON=C 3,663,594 5/1972 Brown et al. J 71--98 XE (3H3 "3,646,062' 2/1972 Fridinger et a1. zeo-sge c GLENNON H. HOLLRAH, Primary Examiner wherein X is hydrogen, lower alkyl, lower alkoxy, nitro 10 I ULS, CL

chlorine, bromine or iodine, R and R are each lower alkyl 424. 29 and n is an integer of 1 to 3'. 

